EP0655273A2 - Process for purification of gases and exhaust gases - Google Patents

Process for purification of gases and exhaust gases Download PDF

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Publication number
EP0655273A2
EP0655273A2 EP95101853A EP95101853A EP0655273A2 EP 0655273 A2 EP0655273 A2 EP 0655273A2 EP 95101853 A EP95101853 A EP 95101853A EP 95101853 A EP95101853 A EP 95101853A EP 0655273 A2 EP0655273 A2 EP 0655273A2
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EP
European Patent Office
Prior art keywords
gases
calcium hydroxide
exhaust gas
substances
extinguishing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP95101853A
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German (de)
French (fr)
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EP0655273A3 (en
Inventor
Hermann Dr. Suchenwirth
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FTU GmbH
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FTU GmbH
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Priority claimed from DE19873716566 external-priority patent/DE3716566A1/en
Priority claimed from DE19883815982 external-priority patent/DE3815982A1/en
Application filed by FTU GmbH filed Critical FTU GmbH
Publication of EP0655273A2 publication Critical patent/EP0655273A2/en
Publication of EP0655273A3 publication Critical patent/EP0655273A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/02—Lime
    • C04B2/04—Slaking
    • C04B2/06—Slaking with addition of substances, e.g. hydrophobic agents ; Slaking in the presence of other compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B01D53/70—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon

Definitions

  • the invention relates to methods for cleaning gases and exhaust gases.
  • dry exhaust gas cleaning is also used. It consists in blowing powdered calcium hydroxide into the exhaust gas stream to be cleaned. The aim is to neutralize the acidic pollutants present in the exhaust gas stream, such as sulfur dioxide, hydrogen chloride and hydrogen fluoride, and to separate the neutral salts that are formed on suitable separating devices, for example electrostatic filters and fabric filters.
  • the dry exhaust gas cleaning is used in different variants.
  • the most important areas of application are the cleaning of the exhaust gases from coal and lignite-fired power plants, waste incineration plants, special waste incineration plants and combustion plants with a wide variety of input materials.
  • the pollutant-containing exhaust gases can be cleaned as far as possible.
  • the consumption of calcium hydroxide is very high.
  • the stoichiometric factor is 3.5 - 6.
  • waste incineration plants are used instead the required 10-12 kg of hydroxide consistently requires more than 30 kg of calcium hydroxide.
  • the moderate efficiency of dry exhaust gas cleaning is due to the fact that the individual calcium hydroxide particles do not react completely. A layer of reaction products forms on the calcium hydroxide, which prevents further penetration of the acidic pollutants to be separated.
  • One method is to mechanically reprocess the separated product, which consists of unreacted calcium hydroxide and the reaction products formed, by grinding after the exhaust gas purification. The purpose of the grinding is to separate the outer, non-reactive layers.
  • Another method provides for the intermediate storage of the reaction product before and after a storage period of 1-2 days for reuse.
  • the essential idea of the invention is that before the extinguishing, during the extinguishing, with the water required for extinguishing and / or after the extinguishing of the quicklime, the reactivity of the calcium hydroxide-increasing substances and / or pollutant-binding and / or catalytically active substances are added.
  • a particularly preferred embodiment of the process according to the invention now consists in adding substances which increase the reactivity of the calcium hydroxide and / or pollutant-binding substances to the water required for the extinguishing of quicklime.
  • the reactivity of the calcium hydroxide can then be changed in a targeted manner.
  • Ca (OH) 2 can be used as a carrier for other pollutant-binding substances.
  • the added substances can then be compounds which themselves act on the pollutants or substances which change the internal structure, structure and surface of the calcium hydroxide.
  • an advantageous embodiment of the method according to the invention consists in adding alkali hydrogen carbonates, alkali hydroxides and / or alkali carbonates as substances to increase the reactivity.
  • alkali hydrogen carbonates alkali hydroxides and / or alkali carbonates as substances to increase the reactivity.
  • the following are particularly suitable: sodium hydroxide, sodium hydrogen carbonate and / or sodium carbonate.
  • a further embodiment of the method according to the invention consists in adding hydrate-forming compounds as reaction-increasing substances.
  • Hydrates are understood to mean inorganic salts on which water is attached in the form of an addition complex. Hydrate-forming compounds which release part or all of the hydrate water at elevated temperature are preferably used here. Dewatering can take place in the exhaust gas stream.
  • An advantageous embodiment of the method according to the invention now consists in that the hydrated calcium hydroxide is subjected to a thermal treatment for the complete or partial release of the hydrated water before being used for exhaust gas purification.
  • the properties of Ca (OH) 2, e.g. Surface, can be changed in a targeted manner.
  • Calcium chloride and magnesium chloride are preferably added as the hydrate-forming compound.
  • Calcium chloride is known to add water to various levels of hydration.
  • a well-known hydrate is the hexahydrate of calcium chloride. This can be dewatered by heating to over 260 degrees C in stages to anhydrous chloride.
  • Anhydrous calcium chloride for its part, again strives to absorb water, so that hardly any water is absorbed into the interior of the calcium hydroxide even during the implementation of the exhaust gas purification and thus the reactivity is considerably increased, for example compared to SO2. If hydrate-forming substances are added to the extinguishing water, it is advisable to add the water required for hydrate formation to the extinguishing water.
  • Another embodiment of the method according to the invention is to add compounds which form hydroxides during the quenching process, which in turn can be dewatered in the temperature range of 50-450 degrees C.
  • hydroxides Almost all metal salts that are added to the extinguishing water form hydroxides during the extinguishing process. However, not all hydroxides can be dewatered in the temperature range of 50-450 degrees C. Drainable hydroxides form e.g. the heavy metal hydroxides.
  • the procedure can now be such that the hydroxide-containing calcium hydroxide is used directly.
  • the active surface of the calcium hydroxide grain can be increased significantly and thus the reactivity can be increased.
  • Hydroxides are preferably used whose dewatering takes place at temperatures up to a maximum of 450 degrees C. Calcium hydroxide begins to drain from 450 degrees C.
  • the hydroxide-forming compounds used are water-soluble iron (II) and / or iron (III) salts, preferably as chlorides.
  • Iron (II) and iron (III) salts form iron hydroxides in the alkaline range. These iron hydroxides can in turn be drained in stages. This dewatering can take place in the exhaust gas stream during exhaust gas purification. However, it is also possible to carry out this elimination of water in whole or in part before use for exhaust gas purification. In this way, water-containing and water-releasing calcium hydroxides, which are nevertheless available as a dry powder, can be produced in a very targeted manner.
  • the iron-containing calcium hydroxides can preferably be used for the separation of nitrogen oxides, also for the simultaneous separation with acidic pollutants.
  • Both the hydroxide-containing and the hydrated calcium hydroxide powders are non-sticky, easily transportable and easy to introduce into the gas stream.
  • Another problem with exhaust gas purification is that, in addition to the acidic pollutants, heavy metals, in particular mercury, are also present in the exhaust gas stream. Different methods are used to separate mercury. With dry exhaust gas purification itself, it has so far not been possible to increase the separation of mercury to such an extent that the prescribed limit values can be safely adhered to.
  • the usual method of reducing the mercury content of the exhaust gas is to lower the temperature of the exhaust gas by adding water to such an extent that mercury is bound to calcium hydroxide.
  • mercury-binding substances preferably hydrogen sulfide, sodium hydrogen sulfide and / or trimercapto-s-triazine (TMT) and the like, are now added to the extinguishing water required to extinguish the quicklime.
  • TMT is preferably used as the sodium salt.
  • the combination of calcium hydroxide with the mercury-binding substances ensures that the substances characterized by a characteristic odor hydrogen sulfide and sodium hydrogen sulfide and odorless calcium sulfide can be used and the neutralization of the acidic pollutants can be carried out together with the binding of mercury. In this way, additional emission control stages can be avoided.
  • An advantageous embodiment of the method according to the invention consists in the fact that not only one group of substances but whole combinations for different pollutants to be separated are added to the extinguishing water.
  • a combination according to the invention which can be used with great advantage consists of sodium hydrogen carbonate, iron (III) chloride and trimercapto-s-triazine (TMT). With such a combination, not only acidic pollutants but also nitrogen oxides and volatile heavy metals, in particular mercury, can be separated.
  • One embodiment of the method according to the invention thus consists in adding both acid-binding and nitrogen-binding as well as heavy metal-binding substances to the extinguishing water and a calcium hydroxide modified in this way to manufacture.
  • Calcium hydroxides which contain oxidizing, reducing, neutralizing and / or heavy metal-containing substances can thus be produced by the process according to the invention.
  • tin and zinc chloride can be added to the extinguishing water, which is then incorporated into the calcium hydroxide.
  • the metal salts can e.g. can be reduced to zinc or tin with hydrogen. This metal, which is finely distributed over the calcium hydroxide, is then preferably used to absorb mercury from the exhaust gas stream.
  • Heavy metals are advantageously used as oxidizing or reducing substances. These are the heavy metals that occur in various oxidation levels, e.g. vanadium, molybdenum, tungsten, manganese, titanium, copper, chromium and vanadium.
  • the heavy metal-containing calcium hydroxides can also be used for further exhaust gas purification.
  • carbon monoxide can be oxidized to carbon dioxide.
  • the hydrocarbons present in the exhaust gas can also be oxidized, so that the total C content is reduced.
  • the substances mentioned activated carbon, brown coal hearth coke, activated aluminum oxide / or silica gel are used in fine distribution as surface-active substances.
  • the effect of these surface-active substances relates to residual contents of organic substances, chlorinated hydrocarbons such as dioxins, hexachlorobenzene, pentachlorophenol and the like, polycondensed aromatic hydrocarbons such as benzo (a) pyrene, dibenz (a, h) anthracene and the like from the exhaust gas stream . to separate.
  • chlorinated hydrocarbons such as dioxins, hexachlorobenzene, pentachlorophenol and the like
  • polycondensed aromatic hydrocarbons such as benzo (a) pyrene, dibenz (a, h) anthracene and the like from the exhaust gas stream .
  • a preferred embodiment of the method according to the invention consists in adding activated carbon, brown coal hearth coke, activated aluminum oxide and / or silica gel in finely divided manner to the extinguishing water of quicklime as surface-active substances.
  • the activated carbon is particularly suitable for binding organic substances and also mercury.
  • Silica gel and aluminum oxide are particularly suitable for polar substances, such as oxidized organic compounds, and inorganic pollutants, such as hydrogen chloride and sulfur dioxide.
  • the method according to the invention can be carried out in such a way that the surface-active substances are acted upon by catalytically active or pollutant-binding substances before they are introduced into the extinguishing process for quicklime.
  • This can be carried out in such a way that the catalytically active or pollutant-binding
  • the surface-active substances are added to the extinguishing water.
  • the surface-active substances adsorb the contents of the extinguishing water.
  • calcium hydroxide and surface-active substances are present in the finest distribution and in the best possible mixture.
  • This idea of the invention can be realized with advantage if the surface-active substances are extinguished with mercury-binding substances, e.g. Sodium sulfide, mercaptans or trimercapto-s-triazine and / or vanadium, tungsten, molybdenum, manganese, iron, nickel, cobalt, chromium and / or titanium compounds.
  • mercury-binding substances e.g. Sodium sulfide, mercaptans or trimercapto-s-triazine and / or vanadium, tungsten, molybdenum, manganese, iron, nickel, cobalt, chromium and / or titanium compounds.
  • the catalytic or mercury-binding substances are then available in a large surface area for exhaust gas purification and are particularly effective.
  • Another embodiment of the method according to the invention is that for the production of reactive calcium hydroxides for gas and exhaust gas purification, the surface-active substances, such as activated carbon, lignite-type oven coke, aluminum oxide, silica gel and the like. mixed with the quicklime and only then is the extinguishing process carried out.
  • the surface-active substances such as activated carbon, lignite-type oven coke, aluminum oxide, silica gel and the like. mixed with the quicklime and only then is the extinguishing process carried out.
  • Mixing can be carried out either in mixing equipment or in mills.
  • Another object of the invention is a process for the purification of gases and exhaust gases from acidic pollutants, such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, hydrocyanic acid and the like.
  • acidic pollutants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, hydrocyanic acid and the like.
  • hydrocarbons, chlorinated hydrocarbons and volatile heavy metals for example mercury, arsenic, antimony, cadmium and thallium in such a way that finely powdered calcium hydroxide is added to the gas or exhaust gas stream, which contains surface-active substances, such as activated carbon, lignite hearth coke, silica gel and / or active aluminum oxide, and that the hydroxide laden with pollutants is separated again on dust separators.
  • the cleaning process of gases can be carried out in a wide temperature range of 200-1000 degrees C. At temperatures above 400 degrees C it is appropriate to use activated aluminum oxide or silica gel as the surface-active substance. All surface-active substances listed are suitable at lower temperatures.
  • the amount of the substances to be used it should be noted that this depends on the amount of the pollutant to be separated and the solubility of the respective substance in water.
  • the upper limit of the substance to be added depends on its solubility in water.
  • the reactivity of Ca (OH) 2 can be increased significantly, i.e. the use of Ca (OH) 2 for the separation of acidic pollutants can be significantly reduced.
  • volatile heavy metals e.g. Mercury, cadmium and the like separate from the exhaust gas flow.
  • a major advantage is the simultaneous separation or concentration reduction of acidic pollutants and nitrogen oxides, which can also be combined with a simultaneous heavy metal separation.
  • additives to the extinguishing water can be used to change and specifically influence physical properties such as surface, flow behavior, distributability in the exhaust gas stream and the like.
  • a further preferred embodiment of the method according to the invention is characterized in that when using metal salts with chloride, nitrite and / or nitrate as the anion accelerating the quenching process, metal salts with sulfate, hydrogen carbonate, phosphate and / or hydroxide are added as the anion inhibiting the quenching process.
  • calcium chloride accelerates the extinguishing process very strongly.
  • the rapid course of the extinguishing reaction can be inhibited by combination with iron sulfate and the extinguishing time can be set as desired.
  • the selection of the salts with an accelerating character and those with an inhibition must be made in such a way that no precipitation reactions occur in the solution in the extinguishing water. It has proven to be advantageous to use the alkali, magnesium, calcium, aluminum and iron chlorides with iron and / or aluminum sulfate as the salts which inhibit the quenching process.
  • the modified Ca (OH) 2 compounds produced according to the invention can be used not only for binding pollutants but also as catalysts in oxidation and reduction processes.
  • 28g freshly made quicklime is extinguished with 18g water.
  • the time to reach 90 degrees C is 13 seconds. If 0.4 g aluminum sulfate x 18H2O is added to the extinguishing water, 18 seconds are required to reach 90 degrees Celsius.
  • the extinguishing time can be reduced by more than 50% if the specified amount of aluminum sulfate 0.2 g of iron (III) chloride x 6H 2 O are added. Then the time required to reach 90 degrees C is only 11 seconds.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Glass Compositions (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

(A) In the prodn. of reactive calcium hydroxide for (waste) gas purificn., the novelty is that reactivity increasing materials and/or noxious material-binding materials and/or catalytically acting materials are added prior to slaking, during slaking, to the water required for slaking and/or after slaking. (B) Use of the calcium hydro produced by process (A), for sepn. of acidic noxious materials and/or heavy metals and/or NOx and/or CO and/or organic materials from (waste) gases, is also claimed. (C) Purificn. of (waste) gases, to remove acidic gases (e.g. HCl, HF, SO2 and HCN), NOx, (chlorinated) hydrocarbons, organic cpds. and volatile heavy metals (e.g. Hg, As, Sb, Cd and Tl), comprises mixing the gases with the calcium hydroxide produced by process (A), at 20-1200 deg.C and then sepg. the solids in dust precipitators.

Description

Die Erfindung betrifft Verfahren zur Reinigung von Gasen und Abgasen.The invention relates to methods for cleaning gases and exhaust gases.

Auf dem Gebiet der Abgasreinigung kommen zahlreiche Verfahren zur Anwendung. Neben der nassen Abgasreinigung kommt auch die trockene Abgasreinigung zum Einsatz. Sie besteht darin, in den zu reinigenden Abgasstrom pulverförmiges Calciumhydroxid einzublasen. Ziel ist, die im Abgasstrom vorhandenen sauren Schadstoffe, wie Schwefeldioxid,Chlorwasserstoff und Fluorwasserstoff zu neutralisieren und die gebildeten Neutralsalze an geeigneten Abscheidevorrichtungen, zum Beispiel Elektrofiltern und Gewebefiltern abzuscheiden.Numerous processes are used in the field of exhaust gas purification. In addition to wet exhaust gas cleaning, dry exhaust gas cleaning is also used. It consists in blowing powdered calcium hydroxide into the exhaust gas stream to be cleaned. The aim is to neutralize the acidic pollutants present in the exhaust gas stream, such as sulfur dioxide, hydrogen chloride and hydrogen fluoride, and to separate the neutral salts that are formed on suitable separating devices, for example electrostatic filters and fabric filters.

Die trockene Abgasreinigung wird in verschiedenen Varianten angewandt. Die wesentlichsten Einsatzgebiete sind die Reinigung der Abgase von Kohle- und Braunkohlekraftwerken, Müllverbrennungsanlagen, Sondermüllverbrennungsanlagen und Feuerungsanlagen mit unterschiedlichstem Einsatzmaterial.The dry exhaust gas cleaning is used in different variants. The most important areas of application are the cleaning of the exhaust gases from coal and lignite-fired power plants, waste incineration plants, special waste incineration plants and combustion plants with a wide variety of input materials.

Mit Hilfe der trockenen Abgasreinigung lassen sich die schadstoffhaltigen Abgase weitestgehend reinigen. Von Nachteil ist jedoch, daß der Verbrauch an Calciumhydroxid sehr hoch ist. Im allgemeinen beträgt der stöchiometrische Faktor 3,5 - 6. So werden z.B. bei Abfallverbrennungsanlagen anstelle der erforderlichen 10-12 kg Hydroxid durchwegs mehr als 30 kg Calciumhydroxid benötigt. Der mäßige Wirkungsgrad der trockenen Abgasreinigung ist darauf zurückzuführen, daß die einzelnen Calciumhydroxidteilchen nicht vollständig durchreagieren. Auf dem Calciumhydroxid bildet sich eine Schicht aus Reaktionsprodukten, die das weitere Eindringen der abzuscheidenden sauren Schadstoffe verhindert.With the help of dry exhaust gas cleaning, the pollutant-containing exhaust gases can be cleaned as far as possible. However, it is disadvantageous that the consumption of calcium hydroxide is very high. In general, the stoichiometric factor is 3.5 - 6. For example, waste incineration plants are used instead the required 10-12 kg of hydroxide consistently requires more than 30 kg of calcium hydroxide. The moderate efficiency of dry exhaust gas cleaning is due to the fact that the individual calcium hydroxide particles do not react completely. A layer of reaction products forms on the calcium hydroxide, which prevents further penetration of the acidic pollutants to be separated.

Es ist immer wieder versucht worden, den hohen Calciumhydroxidverbrauch zu senken. Ein Verfahren besteht darin, nach der Abgasreinigung das abgeschiedene Produkt, das aus nicht umgesetztem Calciumhydroxid und den gebildeten Reaktionsprodukten besteht, mechanisch durch Mahlen wiederaufzubereiten. Sinn und Zweck des Mahlens besteht darin, die äußeren nicht reaktionsfähigen Schichten abzutrennen. Ein weiteres Verfahren sieht eine Zwischenlagerung des Reaktionsproduktes vor und nach einer Lagerung von 1-2 Tagen ein erneuter Einsatz.There have been repeated attempts to reduce the high calcium hydroxide consumption. One method is to mechanically reprocess the separated product, which consists of unreacted calcium hydroxide and the reaction products formed, by grinding after the exhaust gas purification. The purpose of the grinding is to separate the outer, non-reactive layers. Another method provides for the intermediate storage of the reaction product before and after a storage period of 1-2 days for reuse.

Alle diese Verfahren sind jedoch von einer ungenügenden Wirksamkeit hinsichtlich der Steigerung der Reaktionsfähigkeit von Calciumhydroxid gekennzeichnet.
Unter Steigerung der Reaktionsfähigkeit des Ca(OH)₂ wird die Verringerung der Ca(OH)₂-Menge zur Erreichung eines bestimmten Abscheidegrades der sauren Schadstoffe verstanden. Ein niedriger stöchiometrischer Faktor Ca(OH)₂/saure Schadstoffe bedeutet eine höhere Reaktionsfähigkeit.However, all of these methods are characterized by insufficient effectiveness in increasing the reactivity of calcium hydroxide.
Increasing the reactivity of Ca (OH) ₂ means reducing the amount of Ca (OH) ₂ to achieve a certain degree of separation of the acidic pollutants. A lower stoichiometric factor Ca (OH) ₂ / acidic pollutants means a higher reactivity.

Es besteht deshalb ein erhebliches Interesse, Calciumhydroxidverbindungen herzustellen, die eine erhöhte Reaktionsfähigkeit gegenüber den sauren Schadstoffen der Abgase aufweisen. Weiterhin besteht ein Interesse daran, neben den sauren Schadstoffen des Abgases noch weitere Stoffe aus dem Abgas abzuscheiden. Dies sind insbesondere die Stickstoffoxide und das flüchtige Schwermetall Quecksilber. Von Interesse hierbei ist, die Abscheibung dieser Stoffe nicht in separaten Stufen sondern einstufig zusammen mit den sauren Schadstoffen durchzuführen.There is therefore considerable interest in producing calcium hydroxide compounds which have an increased reactivity to the acidic pollutants of the exhaust gases. There is also an interest in separating other substances from the exhaust gas in addition to the acidic pollutants in the exhaust gas. These are in particular the nitrogen oxides and the volatile heavy metal mercury. It is of interest here that these substances are not separated off in separate stages but in one step together with the acidic pollutants.

Weiterhin wäre es von Vorteil, zusammen mit der Abscheidung saurer Schadstoffe auch den Gehalt an CO und/oder Gesamt-C zu verringern.It would also be advantageous to also reduce the CO and / or total C content together with the separation of acidic pollutants.

Der wesentliche Erfindungsgedanke, wie er in Anspruch 1 niedergelegt ist, besteht darin, daß vor dem Löschen, während des Löschens, mit dem zum Löschen erforderlichen Wasser und/oder nach dem Löschen des Branntkalkes die Reaktionsfähigkeit des Calciumhydroxids steigernde Stoffe und/oder schadstoffbindende und/oder katalytisch wirkende Stoffe zugesetzt werden.The essential idea of the invention, as set out in claim 1, is that before the extinguishing, during the extinguishing, with the water required for extinguishing and / or after the extinguishing of the quicklime, the reactivity of the calcium hydroxide-increasing substances and / or pollutant-binding and / or catalytically active substances are added.

Eine besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht nun darin, daß dem zum Löschen von Branntkalk erforderlichen Wasser die Reaktionsfähigkeit des Calciumhydroxids steigernde Stoffe und /oder schadstoffbindende Stoffe zugesetzt werden.A particularly preferred embodiment of the process according to the invention now consists in adding substances which increase the reactivity of the calcium hydroxide and / or pollutant-binding substances to the water required for the extinguishing of quicklime.

Mit Hilfe derartiger eingeschleuster Substanzen läßt sich dann die Reaktionsfähigkeit des Calciumhydroxids gezielt verändern.With the help of such infiltrated substances, the reactivity of the calcium hydroxide can then be changed in a targeted manner.

Weiterhin kann Ca(OH)₂ als Träger für andere schadstoffbindende Stoffe benutzt werden.Furthermore, Ca (OH) ₂ can be used as a carrier for other pollutant-binding substances.

Bei den zugesetzten Stoffen kann es sich dann um Verbindungen handeln, die selbst auf die Schadstoffe einwirken, oder um Substanzen, die den inneren Aufbau, die Struktur und die Oberfläche des Calciumhydroxids verändern.The added substances can then be compounds which themselves act on the pollutants or substances which change the internal structure, structure and surface of the calcium hydroxide.

Eine vorteilhafte Ausführung des erfindungsgemäßen Verfahrens besteht nun darin, daß Stoffe zugesetzt werden, die die Bindung saurer Schadstoffe, wie HCl, HF, SO₂, SO₃, NO₂, HCN, Phenole, Carbonsäuren und dergl. begünstigen.An advantageous embodiment of the method according to the invention is now that substances are added which favor the binding of acidic pollutants, such as HCl, HF, SO₂, SO₃, NO₂, HCN, phenols, carboxylic acids and the like.

Unter diesen Stoffen werden vornehmlich Stoffe verstanden, die stark basisch wirken und deshalb bevorzugt mit den sauren Schadstoffen reagieren.These substances are primarily understood to be substances which have a strongly basic action and therefore react preferentially with the acidic pollutants.

Demnach besteht eine vorteilhafte Ausführung des erfindungsgemäßen Verfahrens darin, als Stoffe zur Steigerung der Reaktionsfähigkeit Alkalihydrogencarbonate, Alkalihydroxide und/oder Alkalicarbonate zuzusetzen. Hierzu sind besonders geeignet: Natriumhydroxid, Natriumhydrogencarbonat und/oder Natriumcarbonat.Accordingly, an advantageous embodiment of the method according to the invention consists in adding alkali hydrogen carbonates, alkali hydroxides and / or alkali carbonates as substances to increase the reactivity. The following are particularly suitable: sodium hydroxide, sodium hydrogen carbonate and / or sodium carbonate.

Diese Stoffe werden dem Löschwasser zugesetzt und dringen während des Ablöschprozeßes in das sich bildende Calciumhydroxidteilchen ein. Hierbei kann es auch zu weiteren Umsetzungen mit Calciumhydroxid kommen. Z. B. dürfte sich Natriumhydrogencarbonat aber auch Natriumcarbonat mit Calciumhydroxid anteilig zu Calciumcarbonat unter Freisetzung von Natriumhydroxid umsetzen. Es liegt also bei Anwendung derartiger Stoffe ein komplexes Gemisch der verschiedensten basischen Stoffe vor.These substances are added to the extinguishing water and penetrate into the calcium hydroxide particles that form during the extinguishing process. This can also lead to further reactions with calcium hydroxide. For example, sodium hydrogen carbonate but also sodium carbonate with calcium hydroxide is likely to convert to calcium carbonate with the release of sodium hydroxide. When such substances are used, there is a complex mixture of the most diverse basic substances.

Eine weitere Ausführung des erfindungsgemäßen Verfahrens besteht darin, als reaktionssteigernde Stoffe hydratbildende Verbindungen zuzusetzen. Unter Hydraten werden dabei anorganische Salze verstanden, an denen Wasser in form eines Anlagerungskomplexes angelagert ist. Bevorzugt werden hierbei hydratbildende Verbindungen eingesetzt, die bei erhöhter Temperatur einen Teil oder die Gesamtmenge des Hydratwassers abgeben. Die Entwässerung kann hierbei im Abgasstrom erfolgen.A further embodiment of the method according to the invention consists in adding hydrate-forming compounds as reaction-increasing substances. Hydrates are understood to mean inorganic salts on which water is attached in the form of an addition complex. Hydrate-forming compounds which release part or all of the hydrate water at elevated temperature are preferably used here. Dewatering can take place in the exhaust gas stream.

Eine vorteilhafte Ausführungsform des erfindungsgemäßen Verfahrens besteht nun darin, daß das hydrathaltige Calciumhydroxid vor dem Einsatz zur Abgasreingiung einer thermischen Behandlung zur ganzen oder teilweisen Abgabe des Hydratwasers unterworfen wird. Damit können die Eigenschaften des Ca(OH)₂, z.B. Oberfläche, gezielt verändert werden.An advantageous embodiment of the method according to the invention now consists in that the hydrated calcium hydroxide is subjected to a thermal treatment for the complete or partial release of the hydrated water before being used for exhaust gas purification. The properties of Ca (OH) ₂, e.g. Surface, can be changed in a targeted manner.

Die Anwesenheit von hydrathaltigen Verbindungen im Calciumhydroxidmolekül führt zu einer deutlichen Steigerung der Reaktionsfähigkeit des Calciumhydroxids.The presence of hydrated compounds in the calcium hydroxide molecule leads to a significant increase in the reactivity of the calcium hydroxide.

Als hydratbildende Verbindung werden vorzugsweise Calciumchlorid und Magnesiumchlorid zugesetzt.
Calciumchlorid ist dafür bekannt, daß es Wasser zu verschiedenen Hydratationsstufen anlagert. Ein bekanntes Hydrat ist das Hexahydrat des Calciumchlorids. Dieses kann durch Erhitzen auf über 260 Grad C in Stufen zu wasserfreiem Chlorid entwässert werden. Wasserfreies Calciumchlorid seinerseits hat wieder das Bestreben, Wasser aufzunehmen, so daß auch während der Umsetzung bei der Abgasreinigung in das Innere des Calciumhydroxids kaum Wasser aufgenommen wird und damit die Reaktionsfähigkeit eine erhebliche Steigerung erfährt, z.B. gegenüber SO₂.
Werden hydratbildende Stoffe dem Löschwasser zugesetzt, so ist es zweckmäßig, das zur Hydratbildung erforderliche Wasser dem Löschwasser zuzugeben.Calcium chloride and magnesium chloride are preferably added as the hydrate-forming compound.
Calcium chloride is known to add water to various levels of hydration. A well-known hydrate is the hexahydrate of calcium chloride. This can be dewatered by heating to over 260 degrees C in stages to anhydrous chloride. Anhydrous calcium chloride, for its part, again strives to absorb water, so that hardly any water is absorbed into the interior of the calcium hydroxide even during the implementation of the exhaust gas purification and thus the reactivity is considerably increased, for example compared to SO₂.
If hydrate-forming substances are added to the extinguishing water, it is advisable to add the water required for hydrate formation to the extinguishing water.

Eine weitere Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, Verbindungen zuzusetzen, die während des Löschprozeßes Hydroxide bilden, die ihrerseits im Temperaturbereich von 50-450 Grad C entwässerbar sind.Another embodiment of the method according to the invention is to add compounds which form hydroxides during the quenching process, which in turn can be dewatered in the temperature range of 50-450 degrees C.

Nahezu alle Metallsalze, die dem Löschwasser zugesetzt werden, bilden beim Löschprozeß Hydroxide. Nicht alle Hydroxide sind jedoch im Temperaturbereich von 50-450 Grad C entwässerbar. Entwässerbare Hydroxide bilden z.B. die Schwermetallhydroxide.Almost all metal salts that are added to the extinguishing water form hydroxides during the extinguishing process. However, not all hydroxides can be dewatered in the temperature range of 50-450 degrees C. Drainable hydroxides form e.g. the heavy metal hydroxides.

Bei der Durchführung des erfindungsgemäßen Verfahrens kann nun so vorgegangen werden, daß das hydroxidhaltige Calciumhydroxid direkt eingesetzt wird. Andererseits kann es jedoch auch zweckmäßig sein, das hydroxidhaltige Calciumhydroxid vor dem Einsatz zur Abgasreingiung einer thermischen Behandlung zur ganzen oder teilweisen Entwässerung zu unterwerfen.When carrying out the process according to the invention, the procedure can now be such that the hydroxide-containing calcium hydroxide is used directly. On the other hand, however, it may also be expedient to subject the calcium hydroxide containing hydroxide to a thermal treatment for complete or partial dewatering before use for exhaust gas purification.

Durch die ganze oder teilweise Entwässerung kann die aktive Oberfläche des Calciumhydroxidkorns deutlich erhöht und damit die Reaktionsfähigkeit gesteigert werden.Through the complete or partial dewatering, the active surface of the calcium hydroxide grain can be increased significantly and thus the reactivity can be increased.

Vorzugsweise werden Hydroxide eingesetzt, deren Entwässerung bei Temperaturen bis maximal 450 Grad C erfolgt. Ab 450 Grad C setzt die Entwässerung des Calciumhydroxids ein.Hydroxides are preferably used whose dewatering takes place at temperatures up to a maximum of 450 degrees C. Calcium hydroxide begins to drain from 450 degrees C.

Erfindungsgemäß werden als hydroxidbildende Verbindungen - wasserlösliche Eisen(II)- und/oder Eisen(III)-Salze, vorzugsweise als Chloride, eingesetzt. Eisen(II)- und Eisen (III)-Salze bilden im alkalischen Bereich Eisenhydroxide. Diese Eisenhydroxide können ihrerseits stufenweise entwässert werden. Diese Entwässerung kann dabei während der Abgasreinigung im Abgasstrom erfolgen. Es ist jedoch auch möglich, diese Abspaltung von Wasser ganz oder teilweise vor dem Einsatz zur Abgasreinigung durchzuführen. Auf diese Art und Weise können ganz gezielt wasserhaltige und wasserabgebende Calciumhydroxide, die trotzdem als trockenes Pulver vorliegen, hergestellt werden.According to the invention, the hydroxide-forming compounds used are water-soluble iron (II) and / or iron (III) salts, preferably as chlorides. Iron (II) and iron (III) salts form iron hydroxides in the alkaline range. These iron hydroxides can in turn be drained in stages. This dewatering can take place in the exhaust gas stream during exhaust gas purification. However, it is also possible to carry out this elimination of water in whole or in part before use for exhaust gas purification. In this way, water-containing and water-releasing calcium hydroxides, which are nevertheless available as a dry powder, can be produced in a very targeted manner.

Die eisenhaltigen Calciumhydroxide lassen sich bevorzugt zur Abscheidung von Stickstoffoxiden verwenden, auch zur simultanen Abscheidung mit sauren Schadstoffen.The iron-containing calcium hydroxides can preferably be used for the separation of nitrogen oxides, also for the simultaneous separation with acidic pollutants.

Sowohl bei den hydroxidhaltigen, als auch bei den hydrathaltigen Calciumhydroxidpulvern handelt es sich um nichtklebende, leicht transportfähige und leicht in den Gasstrom einzubringende Pulver.Both the hydroxide-containing and the hydrated calcium hydroxide powders are non-sticky, easily transportable and easy to introduce into the gas stream.

Ein weiteres Problem der Abgasreinigung besteht darin, daß neben den sauren Schadstoffen auch noch Schwermetalle, insbesondere Quecksilber,im Abgasstrom vorliegen. Zur Abscheidung von Quecksilber werden unterschiedliche Methoden angewandt. Bei der trockenen Abgasreinigung selbst ist es bisher nicht möglich gewesen, die Abscheidung von Quecksilber so weit zu steigern, daß die vorgeschriebenen Grenzwerte sicher eingehalten werden können. Das übliche Verfahren, den Quecksilbergehalt des Abgases zu vermindern, besteht darin, die Temperatur des Abgases durch Zugabe von Wasser so weit abzusenken, daß eine Bindung von Quecksilber an Calciumhydroxid erfolgt.Another problem with exhaust gas purification is that, in addition to the acidic pollutants, heavy metals, in particular mercury, are also present in the exhaust gas stream. Different methods are used to separate mercury. With dry exhaust gas purification itself, it has so far not been possible to increase the separation of mercury to such an extent that the prescribed limit values can be safely adhered to. The usual method of reducing the mercury content of the exhaust gas is to lower the temperature of the exhaust gas by adding water to such an extent that mercury is bound to calcium hydroxide.

Dieses Verfahren hat jedoch den Nachteil, daß nach wie vor deutliche Mengen an Quecksilber im Abgas bleiben und dabei unkontrollierten Wasserzugaben Störungen in den nachgeschalteten Abscheidevorrichtungen auftreten können.However, this method has the disadvantage that significant amounts of mercury remain in the exhaust gas and uncontrolled additions of water can cause faults in the downstream separating devices.

Erfindungsgemäß werden nun dem zum Löschen des Branntkalkes erforderlichen Löschwasser quecksilberbindende Stoffe, vorzugsweise Schwefelwasserstoff, Natriumhydrogensulfid und/oder Trimercapto-s-triazin(TMT) und dergl. zugesetzt. TMT wird bevorzugt als Natriumsalz eingesetzt.According to the invention, mercury-binding substances, preferably hydrogen sulfide, sodium hydrogen sulfide and / or trimercapto-s-triazine (TMT) and the like, are now added to the extinguishing water required to extinguish the quicklime. TMT is preferably used as the sodium salt.

Durch die Kombination von Calciumhydroxid mit den quecksilberbindenden Stoffen wird erreicht, daß die durch einen charakteristischen Geruch ausgezeichneten Stoffe Schwefelwasserstoff und Natriumhydrogensulfid inform geruchloser Calciumsulfide eingesetzt werden können und die Neutralisation der sauren Schadstoffe gemeinsam mit der Bindung von Quecksilber durchgeführt werden kann. Auf diese Art und Weise können zusätzliche Abgasreinigungsstufen vermieden werden.The combination of calcium hydroxide with the mercury-binding substances ensures that the substances characterized by a characteristic odor hydrogen sulfide and sodium hydrogen sulfide and odorless calcium sulfide can be used and the neutralization of the acidic pollutants can be carried out together with the binding of mercury. In this way, additional emission control stages can be avoided.

Durch die Anwesenheit von Eisenverbindungen im Calciumhydroxid werden die Stickoxide zu höheren Stickoxiden oxidiert und können dann mit Calciumhydroxid gebunden werden. Durch die Anwendung des erfindungsgemäßen Verfahrens können demnach zahlreiche Schadstoffe aus dem Abgasstrom entfernt werden. Eine vorteilhafte Ausführungsform des erfindungsgemäßen Verfahrens besteht nun darin, daß dem Löschwasser nicht nur eine Stoffgruppe sondern ganze Kombinationen für verschiedene abzuscheidende Schadstoffe zugesetzt werden. Eine erfindungsgemäße mit großem Vorteil einzusetzende Kombination besteht aus Natriumhydrogencarbonat, Eisen(III)-chlorid und Trimercapto-s-triazin(TMT). Mit einer derartigen Kombination können nicht nur saure Schadstoffe sondern auch Stickstoffoxide und leicht flüchtige Schwermetalle insbesondere Quecksilber abgeschieden werden.Due to the presence of iron compounds in the calcium hydroxide, the nitrogen oxides are oxidized to higher nitrogen oxides and can then be bound with calcium hydroxide. Accordingly, numerous pollutants can be removed from the exhaust gas stream by using the method according to the invention. An advantageous embodiment of the method according to the invention consists in the fact that not only one group of substances but whole combinations for different pollutants to be separated are added to the extinguishing water. A combination according to the invention which can be used with great advantage consists of sodium hydrogen carbonate, iron (III) chloride and trimercapto-s-triazine (TMT). With such a combination, not only acidic pollutants but also nitrogen oxides and volatile heavy metals, in particular mercury, can be separated.

Eine Ausführungsform des erfindungsgemäßen Verfahrens besteht also darin, sowohl säurebindende als auch stickstoffbindende wie auch schwermetallbindende Stoffe gemeinsam dem Löschwasser zuzusetzen und ein derartig modifiziertes Calciumhydroxid herzustellen.One embodiment of the method according to the invention thus consists in adding both acid-binding and nitrogen-binding as well as heavy metal-binding substances to the extinguishing water and a calcium hydroxide modified in this way to manufacture.

Nach dem erfindungsgemäßen Verfahren können also Calciumhydroxide hergestellt werden, die oxidierende, reduzierende, neutralisierende und/oder schwermetallhaltige Stoffe enthalten. So ist es beispielsweise möglich, dem Löschwasser Zinn- und Zinkchlorid zuzusetzen, das dann in das Calciumhydroxid eingebunden wird. Die Metallsalze können z.B. mit Wasserstoff zu Zink bzw. Zinn reduziert werden. Dieses über das Calciumhydroxid fein verteilte Metall dient dann bevorzugt zur Aufnahme von Quecksilber aus dem Abgasstrom.Calcium hydroxides which contain oxidizing, reducing, neutralizing and / or heavy metal-containing substances can thus be produced by the process according to the invention. For example, it is possible to add tin and zinc chloride to the extinguishing water, which is then incorporated into the calcium hydroxide. The metal salts can e.g. can be reduced to zinc or tin with hydrogen. This metal, which is finely distributed over the calcium hydroxide, is then preferably used to absorb mercury from the exhaust gas stream.

Als oxidierende oder reduzierende Stoffe sind mit Vorteil Schwermetalle einzusetzen. Es handelt sich dabei um die Schwermetalle, die in verschiedenen Oxidationsstufen vorkommen,z.B.Vanadin, Molybdän, Wolfram, Mangan, Titan, Kupfer, Chrom und Vanadin.Heavy metals are advantageously used as oxidizing or reducing substances. These are the heavy metals that occur in various oxidation levels, e.g. vanadium, molybdenum, tungsten, manganese, titanium, copper, chromium and vanadium.

Diese Schwermetalle werden dem Löschwasser in Form wasserlöslicher Salze zugesetzt und können nach der Aufnahme in das Calciumhydroxid noch einer Reduktion oder Oxidation unterworfen werden.These heavy metals are added to the extinguishing water in the form of water-soluble salts and can be subjected to a reduction or oxidation after absorption in the calcium hydroxide.

Die schwermetallhaltigen Calciumhydroxide können neben der üblichen "Entsäuerung" des Abgases auch zur weitergehenden Abgasreingiung verwendet werden. Z.B. kann Kohlenmonoxid zu Kohlendioxid oxidiert werden. Oxidiert werden können auch die im Abgas vorhandenen Kohlenwasserstoffe, so daß es zur Absenkung des Gesamt-C-Gehaltes kommt.In addition to the usual "deacidification" of the exhaust gas, the heavy metal-containing calcium hydroxides can also be used for further exhaust gas purification. E.g. carbon monoxide can be oxidized to carbon dioxide. The hydrocarbons present in the exhaust gas can also be oxidized, so that the total C content is reduced.

Als oberflächenaktive Substanzen kommen die erwähnten Substanzen Aktivkohle, Braunkohlen-Herdofenkoks, aktiviertes Aluminiumoxid /oder Kieselgel in feiner Verteilung zur Anwendung. Die Wirkung dieser oberflächenaktiven Substanzen bezieht sich darauf, aus dem Abgasstrom Restgehalte an organischen Stoffen, an chlorierten Kohlenwasserstoffen, wie Dioxinen, Hexachlorbenzol, Pentachlorphenol udgl., an polykondensierten aromatischen Kohlenwasserstoffen, wie Benzo(a)pyren, Dibenz(a,h)anthracen udgl. abzuscheiden. Diese Stoffe kommen in Gasen und Abgasströmen im allgemeinen in äußerst geringer Konzentration vor. Deren Abscheidung an herkömmlichen Abscheidevorrichtungen, sei es nun in Wäschern oder an elektrostatischen Abscheidern oder an Gewebefiltern,macht Schwierigkeiten. Bei Einsatz von Calciumhydroxid, das noch oberflächenaktive Substanzen enthält, lassen sich diese Spurenstoffe an die oberflächenaktiven Substanzen binden und damit aus dem Abgasstrom entfernen.The substances mentioned activated carbon, brown coal hearth coke, activated aluminum oxide / or silica gel are used in fine distribution as surface-active substances. The effect of these surface-active substances relates to residual contents of organic substances, chlorinated hydrocarbons such as dioxins, hexachlorobenzene, pentachlorophenol and the like, polycondensed aromatic hydrocarbons such as benzo (a) pyrene, dibenz (a, h) anthracene and the like from the exhaust gas stream . to separate. These substances are extremely common in gases and exhaust gas streams low concentration. Their separation on conventional separation devices, be it in washers or on electrostatic separators or on fabric filters, creates difficulties. When using calcium hydroxide, which still contains surface-active substances, these trace substances can be bound to the surface-active substances and thus removed from the exhaust gas stream.

Ein weiteres Problem der Abscheidung von umwelttoxischen Stoffen sind die Schwermetalle. Hierbei sind es insbesondere Quecksilber, Arsen, Antimon und Thallium, die schon im Temperaturbereich von 20-200 Grad C sehr flüchtig sind. Deren Abscheidung erfolgt aus Abgasen nach dem Stand der Technik derart, daß der Abgasstrom möglichst weit abgekühlt wird, so daß es zur Kondensation des Wassers kommt. Dieses Abkühlen erfordert nicht nur eigene Vorrichtungen sondern auch Energie.
Durch die oberflächenaktiven Substanzen lassen sich die leicht flüchtigen Schwermetalle auch bei Temperaturen von 100-200 Grad C binden und abscheiden.
Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, als oberflächenaktive Substanzen Aktivkohle, Braunkohlen-herdofenkoks, aktiviertes Aluminiumoxid und/oder Kieselgel in fein verteilter Art dem Löschwasser von Branntkalk zuzusetzen.Another problem with the separation of environmentally toxic substances is the heavy metals. It is especially mercury, arsenic, antimony and thallium that are very volatile even in the temperature range of 20-200 degrees Celsius. They are separated from exhaust gases according to the prior art in such a way that the exhaust gas stream is cooled as far as possible, so that the water condenses. This cooling requires not only your own devices but also energy.
Thanks to the surface-active substances, the volatile heavy metals can be bound and separated even at temperatures of 100-200 degrees Celsius.
A preferred embodiment of the method according to the invention consists in adding activated carbon, brown coal hearth coke, activated aluminum oxide and / or silica gel in finely divided manner to the extinguishing water of quicklime as surface-active substances.

Diese oberflächenaktive Stoffe sind zur Durchführung des erfindungsgemäßen Verfahrens besonders geeignet. Die Aktivkohle eignet sich besonders zur Bindung von organischen Substanzen und auch von Quecksilber. Kieselgel und Aluminiumoxid sind für polare Substanzen, wie oxidierte organische Verbindungen, und anorganische Schadstoffe, wie Chlorwasserstoff und Schwefeldioxid besonders geeignet.These surface-active substances are particularly suitable for carrying out the method according to the invention. The activated carbon is particularly suitable for binding organic substances and also mercury. Silica gel and aluminum oxide are particularly suitable for polar substances, such as oxidized organic compounds, and inorganic pollutants, such as hydrogen chloride and sulfur dioxide.

Weiterhin kann das erfidnungsgemäße Verfahren derart durchgeführt werden, daß die oberflächenaktiven Substanzen bevor sie in den Löschprozeß für Branntkalk eingebracht werden, mit katalytisch wirkenden oder schadstoffbindenden Substanzen beaufschlagt werden. Dies kann derart durchgeführt werden, daß die katalytisch wirkenden oder schadstoffbindenden Substanzen im Löschwasser vorliegen und die oberflächenaktiven Substanzen zum Löschwasser gegeben werden. Durch längeres Stehen, evtl. über Stunden, adsorbieren die oberflächenaktiven Substanzen die Inhaltstoffe des Löschwassers. Nach dem Durchführen des Löschprozeßes liegen Calciumhydroxid und oberflächenaktive Substanzen in feinster Verteilung und bestens gemischt vor.Furthermore, the method according to the invention can be carried out in such a way that the surface-active substances are acted upon by catalytically active or pollutant-binding substances before they are introduced into the extinguishing process for quicklime. This can be carried out in such a way that the catalytically active or pollutant-binding There are substances in the extinguishing water and the surface-active substances are added to the extinguishing water. By standing for a long time, possibly for hours, the surface-active substances adsorb the contents of the extinguishing water. After the extinguishing process has been carried out, calcium hydroxide and surface-active substances are present in the finest distribution and in the best possible mixture.

Mit Vorteil läßt sich dieser Erfindungsgedanke verwirklichen, wenn den oberflächenaktiven Substanzen vor dem Löschen quecksilberbindende Stoffe, z.B. Natriumsulfid, Mercaptane oder Trimercapto-s-triazin und/oder Vanadin-, Wolfram-, Molybdän-, Mangan-, Eisen-, Nickel-, Kobalt-, Chrom- und/oder Titanverbindungen beaufschlagt werden. Für die Abgasreinigung liegen die katalytisch wirkenden oder quecksilberbindenden Substanzen dann in großer Oberfläche vor und vermögen ihre Wirksamkeit besonders zu entfalten.This idea of the invention can be realized with advantage if the surface-active substances are extinguished with mercury-binding substances, e.g. Sodium sulfide, mercaptans or trimercapto-s-triazine and / or vanadium, tungsten, molybdenum, manganese, iron, nickel, cobalt, chromium and / or titanium compounds. The catalytic or mercury-binding substances are then available in a large surface area for exhaust gas purification and are particularly effective.

Eine weitere Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß zur Herstellung reaktionsfähiger Calciumhydroxide für die Gas- und Abgasreingiung die oberflächenaktiven Substanzen, wie Aktivkohle, Braunkohlen-Herdofenkoks, Aluminiumoxid, Kiesulgel udgl. dem Branntkalk zugemischt und dann erst der Löschprozeß durchgeführt wird.Another embodiment of the method according to the invention is that for the production of reactive calcium hydroxides for gas and exhaust gas purification, the surface-active substances, such as activated carbon, lignite-type oven coke, aluminum oxide, silica gel and the like. mixed with the quicklime and only then is the extinguishing process carried out.

Das Mischen kann entweder in Mischapparaturen oder auch in Mühlen durchgeführt werden.Mixing can be carried out either in mixing equipment or in mills.

Ein weiterer Gegenstand der Erfindung ist noch ein Verfahren zur Reinigung von Gasen und Abgasen von sauer wirkenden Schadstoffen, wie Chlorwasserstoff, Fluorwasserstoff, Schwefeldioxid, Blausäure udgl., von Stickstoffoxiden, Kohlenwasserstoffen, chlorierten Kohlenwasserstoffen und flüchtigen Schwermetallen, z.B. Quecksilber, Arsen, Antimon, Cadmium und Thallium derart, daß dem Gas- bzw. Abgasstrom feinpulvriges Calciumhydroxid zugesetzt wird, das oberflächenaktive Substanzen, wie Aktivkohle, Braunkohlen-Herdofenkoks, Kieselgel und/oder aktives Aluminiumoxid enthält und daß das mit Schadstoffen beladene Hydroxid an Staubabscheidevorrichtungen wieder abgeschieden wird.Another object of the invention is a process for the purification of gases and exhaust gases from acidic pollutants, such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, hydrocyanic acid and the like. From nitrogen oxides, hydrocarbons, chlorinated hydrocarbons and volatile heavy metals, for example mercury, arsenic, antimony, cadmium and thallium in such a way that finely powdered calcium hydroxide is added to the gas or exhaust gas stream, which contains surface-active substances, such as activated carbon, lignite hearth coke, silica gel and / or active aluminum oxide, and that the hydroxide laden with pollutants is separated again on dust separators.

Der Reinigungsprozeß von Gasen kann hierbei in einem weiten Temperaturbereich von 200-1000 Grad C durchgeführt werden. Bei Temperaturen oberhalb 400 Grad C ist es angebracht, als oberflächenaktive Substanz aktiviertes Aluminiumoxid bzw. Kieselgel einzusetzen. Bei tieferen Temperaturen sind alle angeführten oberflächenaktiven Substanzen geeignet.The cleaning process of gases can be carried out in a wide temperature range of 200-1000 degrees C. At temperatures above 400 degrees C it is appropriate to use activated aluminum oxide or silica gel as the surface-active substance. All surface-active substances listed are suitable at lower temperatures.

Es ist allerdings auch möglich und vorteilhaft, das zu reinigende Gas oder Abgas durch eine feste oder bewegte Schicht aus Ca(OH)₂ zu leiten, das wie oben dargelegt hergestellt worden ist.
Als feste Schicht kommt gekörntes Ca(OH)₂ in Frage. Allerdings ist es auch möglich, Ca(OH)₂ auf gekörntes Material aufzubringen und dann zur Reinigung einzusetzen.However, it is also possible and advantageous to pass the gas or exhaust gas to be cleaned through a fixed or moving layer of Ca (OH) ₂, which has been produced as set out above.
Grained Ca (OH) ₂ can be used as a solid layer. However, it is also possible to apply Ca (OH) ₂ to granular material and then use it for cleaning.

Zur Menge der einzusetzenden Stoffe ist festzustellen, daß sich diese nach der Menge des abzuscheidenden Schadstoffes und der Löslichkeit des jeweiligen Stoffes im Wasser richtet. Die Obergrenze des jeweiligen zuzusetzenden Stoffes richtet sich nach dessen Löslichkeit im Wasser.Regarding the amount of the substances to be used, it should be noted that this depends on the amount of the pollutant to be separated and the solubility of the respective substance in water. The upper limit of the substance to be added depends on its solubility in water.

Mit dem nach dem erfindungsgemäßen Verfahren hergestellten Calciumhydroxid kann die Reaktionsfähigkeit des Ca(OH)₂ deutlich gesteigert werden, d.h. der Brauch an Ca(OH)₂ zur Abscheidung saurer Schadstoffe erheblich gesenkt werden. Gleichzeitig lassen sich noch flüchtige Schwermetalle, z.B. Quecksilber, Cadmium udgl. aus dem Abgasstrom abscheiden. Ein erheblicher Vorteil ist auch die simultane Abscheidung oder Konzentrationsminderung von sauren Schadstoffen und Stickstoffoxiden, die auch mit einer gleichzeitigen Schwermetallabscheidung verbunden werden kann.With the calcium hydroxide produced by the process according to the invention, the reactivity of Ca (OH) ₂ can be increased significantly, i.e. the use of Ca (OH) ₂ for the separation of acidic pollutants can be significantly reduced. At the same time, volatile heavy metals, e.g. Mercury, cadmium and the like separate from the exhaust gas flow. A major advantage is the simultaneous separation or concentration reduction of acidic pollutants and nitrogen oxides, which can also be combined with a simultaneous heavy metal separation.

Weiterhin lassen sich durch Zusätze zum Löschwasser physikalische Eigenschaften, wie Oberfläche, Fließverhalten, Verteilungsfähigkeit im Abgasstrom und dergl. verändern und gezielt beeinflussen.Furthermore, additives to the extinguishing water can be used to change and specifically influence physical properties such as surface, flow behavior, distributability in the exhaust gas stream and the like.

Bei der Verwendung von Salzen mit Chlorid als Anion kommt es zu einer starken Beschleunigung des Löschvorganges. Dies kann u.U. dazu führen, daß die gleichmäßige Durchmischung des Branntkalkes mit Wasser und den darin gelösten Substanzen nicht gewährleistet werden kann. Bei der Verwendung der modifizierten Calciumhydroxide zur Gas- und Abgasreinigung besteht dann die Gefahr, daß die Abscheideleistung starken Schwankungen unterworfen ist.
Andererseits führt die Zugabe von Salzen mit Sulfat und Hydroxid als Anion zu einer Hemmung des Löschvorganges. Eine Hemmung des Löschvorganges hat den Nachteil, daß die vorhandenen Löschapparaturen in ihrer Effektivität verschlechtert werden, d.h. die in der Zeiteinheit hergestellte Menge Calciumhydroxid geht zurück. Hinzu kommt noch, daß bei starker Verzögerung des Löschvorganges die Löschtemperatur niedrig bleibt und damit ein Produkt entsteht, das für die Gas- und Abgasreinigung nicht aktiv genug ist.When using salts with chloride as an anion, the quenching process is greatly accelerated. This can possibly lead to the even mixing the quicklime with water and the substances dissolved in it cannot be guaranteed. When using the modified calcium hydroxides for gas and exhaust gas purification, there is then the risk that the separation performance is subject to strong fluctuations.
On the other hand, the addition of salts with sulfate and hydroxide as an anion leads to an inhibition of the extinguishing process. Inhibiting the extinguishing process has the disadvantage that the effectiveness of the existing extinguishing apparatus is impaired, ie the amount of calcium hydroxide produced in the unit of time decreases. In addition, if the extinguishing process is greatly delayed, the extinguishing temperature remains low, resulting in a product which is not active enough for gas and exhaust gas cleaning.

In Weiterbildung des Gegenstandes der Erfindung wird deshalb erfindungsgemäß vorgeschlagen, daß bei Einsatz von Salzen oder Stoffen, die die Löschgeschwindigkeit steigern, noch Salze oder Stoffe zugesetzt werden, die die Löschgeschwindigkeit verlangsamen.In a development of the subject matter of the invention, it is therefore proposed according to the invention that when salts or substances which increase the rate of extinguishing are used, salts or substances which slow the rate of extinguishing are added.

Es wurde gefunden, daß die hemmende Wirkung von Sulfaten z.B. durch die Zugabe von Chloriden wieder aufgehoben werden kann. Das Mischungsverhältnis hemmende zu beschleunigende Salze kann dabei in weiten Grenzen variiert und so eingestellt werden, daß eine Löschzeit nach Wunsch eintritt.It has been found that the inhibitory effects of sulfates e.g. can be canceled by the addition of chlorides. The mixing ratio of inhibiting salts to be accelerated can be varied within wide limits and set so that an extinguishing time occurs as desired.

Eine weitere bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß bei Einsatz von Metallsalzen mit Chlorid, Nitrit und/oder Nitrat als den Löschvorgang beschleunigendes Anion Metallsalze mit Sulfat, Hydrogencarbonat, Phosphat und/oder Hydroxid als den Löschvorgang hemmendes Anion zugesetzt werden.A further preferred embodiment of the method according to the invention is characterized in that when using metal salts with chloride, nitrite and / or nitrate as the anion accelerating the quenching process, metal salts with sulfate, hydrogen carbonate, phosphate and / or hydroxide are added as the anion inhibiting the quenching process.

Zum Beispiel beschleunigt Calciumchlorid den Löschvorgang sehr stark. Der rasche Verlauf der Löschreaktion kann durch Kombination mit Eisensulfat gehemmt und die Löschzeit nach Wahl eingestellt werden. Die Auswahl der Salze mit Beschleunigungscharakter und der mit Hemmung muß so erfolgen, daß bei der Lösung im Löschwasser keine Fällungsreaktionen eintreten.
Als vorteilhaft hat es sich erwiesen, die Alkali-, Magnesium-, Calcium-, Aluminium- und Eisenchloride mit Eisen- und/oder Aluminiumsulfat als den Löschvorgang hemmende Salze einzusetzen.For example, calcium chloride accelerates the extinguishing process very strongly. The rapid course of the extinguishing reaction can be inhibited by combination with iron sulfate and the extinguishing time can be set as desired. The selection of the salts with an accelerating character and those with an inhibition must be made in such a way that no precipitation reactions occur in the solution in the extinguishing water.
It has proven to be advantageous to use the alkali, magnesium, calcium, aluminum and iron chlorides with iron and / or aluminum sulfate as the salts which inhibit the quenching process.

Außerdem wurde gefunden, daß sich das erfindungsgemäße Verfahren mit Vorteil anwenden läßt, wenn die Löschgeschwindigkeit steigernde und die Löschgeschwindigkeit hemmende Salze im Gewichtsverhältnis 1:5 bis 5:1 eingesetzt werden.It has also been found that the process according to the invention can be used with advantage if the quenching rate-increasing and the quenching-rate-inhibiting salts are used in a weight ratio of 1: 5 to 5: 1.

Die erfindungsgemäß hergestellten modifizierten Ca(OH)₂-Verbindungen lassen sich nicht nur zur Schadstoffbindung sondern auch als Katalysatoren bei Oxidations- und Reduktionsvorgängen einsetzen.The modified Ca (OH) ₂ compounds produced according to the invention can be used not only for binding pollutants but also as catalysts in oxidation and reduction processes.

Beispiel 1example 1

25 g CaO wurden mit 13,5 g Wasser gelöscht. Es fiel ein feines weißes Pulver an.
In einem Glasreaktor wurden durch 253 mg dieses Materials bei 170 Grad C 11,5 l eines Abgases folgender Zusammensetzung geleitet: - Sticksktoff 80 Vol.-% - Sauerstoff 20 Vol.-% - Feuchte 262 mg/l - HCl-Gehalt 22,1 mg/l
21,1 % des zugegebenen HCl wurden von Ca(OH)₂ absorbiert.25 g of CaO were quenched with 13.5 g of water. A fine white powder was obtained.
In a glass reactor, 11.5 liters of an exhaust gas of the following composition were passed through 253 mg of this material at 170 degrees C. - nitrogen 80 vol .-% - oxygen 20 vol .-% - damp 262 mg / l - HCl content 22.1 mg / l
21.1% of the added HCl was absorbed by Ca (OH) ₂.

Beispiel 2Example 2

28 g CaO wurden mit 16,56 Wasser gelöscht, dem 1,4 g CaC1₂ zugesetzt worden waren.
Es fiel ein feines Pulver an.
In einem Glasreaktor wurden durch 274 mg dieses Materials, das 253 mg reinem Ca(OH)₂ entsprach, bei 167 Grad C 12,75 l eines Abgases folgender Zusammensetzung geleitet: - Stickstoff 80 Vol.-% - Sauerstoff 20 Vol.-% - Feuchte 235 mg/l - HCl-Gehalt 19,8 mg/l
23,7 % des zugegebenen HCl wurden von Ca(OH)₂ absorbiert. Dies bedeutet eine um 12,3 % erhöhte HCl-Abscheidung gegenüber Beispiel 1.28 g of CaO were quenched with 16.56 water, 1.4 g of CaC1₂ had been added.
A fine powder was obtained.
In a glass reactor, 274 mg of this material, which corresponded to 253 mg of pure Ca (OH) ₂, passed 12.75 l of an exhaust gas of the following composition at 167 ° C: - nitrogen 80 vol .-% - oxygen 20 vol .-% - damp 235 mg / l - HCl content 19.8 mg / l
23.7% of the added HCl was absorbed by Ca (OH) ₂. This means a 12.3% increase in HCl separation compared to Example 1.

Beispiel 3Example 3

28 g CaO wurden mit 15,2 g Wasser gelöscht, dem 2,3 g FeCl₃ x6H₂O zugesetzt worden waren.
Es fiel ein feines Pulver von schwach rosa Färbung an. In einem Glasreaktor wurden durch 277 mg dieses Materials, das 253 mg Ca(OH)₂ entsprach, bei 166 Grad C 12 l eines Abgases folgender Zusammensetzung geleitet: - Stickstoff 80 Vol.-% - Sauerstoff 20 Vol.-% - Feuchte 250 mg/l - HCl-Gehalt 21 mg/l
28,1 % des zugegebenen HCl wurden von Ca(OH)₂ absorbiert. Dies bedeutet eine um 33% erhöhte HCl-Abscheideleistung gegenüber Beispiel 1 !28 g CaO were quenched with 15.2 g water, to which 2.3 g FeCl₃ x6H₂O had been added.
A fine powder with a pale pink color was obtained. In a glass reactor, 12 l of an exhaust gas of the following composition were passed through 277 mg of this material, which corresponded to 253 mg of Ca (OH) ₂, at 166 ° C: - nitrogen 80 vol .-% - oxygen 20 vol .-% - damp 250 mg / l - HCl content 21 mg / l
28.1% of the added HCl was absorbed by Ca (OH) ₂. This means a 33% higher HCl separation performance compared to example 1!

Beispiel 4Example 4

28 g Branntkalk wurden mit 15,2 g Wasser, in dem 1,4 g Aktivkohle mit 700 m ²/g aktiver Oberfläche suspendiert worden waren, gelöscht. Es entstand ein graues Pulver, das gute Fließfähigkeit aufwies.
Über 252 mg dieser Substanz in fester Schicht wurde bei einer Temperatur von 149 Grad C ein Gas geleitet, das folgende Kennzeichen aufwies: - Feuchte 0,26 g/l - HCl-Gehalt 22,5 mg/l - HgC12-Gehalt 1,29 µg/l
Insgesamt wurden 11,2 l über das modifizierte Ca(OH)₂ geleitet.
Von insgesamt 14,4 µg HgCl₂ wurden 76,5 % an der Aktivkohle absorbiert.28 g quicklime was extinguished with 15.2 g water in which 1.4 g activated carbon with 700 m 2 / g active surface had been suspended. A gray powder resulted, which had good flowability.
A gas was passed over 252 mg of this solid layer substance at a temperature of 149 degrees C, the following Mark had: - damp 0.26 g / l - HCl content 22.5 mg / l - HgC12 content 1.29 µg / l
A total of 11.2 l were passed over the modified Ca (OH) ₂.
Of a total of 14.4 µg HgCl₂, 76.5% was absorbed in the activated carbon.

Beispiel 5Example 5

28 g Branntkalk, der etwa 1 Monat gelagert worden war, wurden mit 15,2 g Wasser versetzt. Nach 40 Sekunden Reaktion wurden 90 Grad C gemessen.
Wurden dem Löschwasser 1,4 g Eisen(III)-sulfatx7H₂O zugesetzt, dann wurden 90 Grad C erst nach 120 Sekunden erreicht. Andererseits führt die Zugabe von 2,3 g Eisen(III)-chloridx6H₂O zum Löschwasser nahezu zu einer Spontanreaktion. Bereits nach 5 Sekunden werden 90 Grad C erreicht. Werden nun dem Löschwasser 0,4 g Eisen(III)-chloridx6H₂O und 0,2 g Eisen(III)-sulfatx7H2O zugesetzt, dann beträgt die Zeit bis zur Erreichung von 90 Grad C rund 50 Sekunden.28 g of quicklime, which had been stored for about 1 month, were mixed with 15.2 g of water. After 40 seconds of reaction, 90 degrees C were measured.
1.4 g of iron (III) sulfatex7H₂O were added to the extinguishing water, then 90 degrees C were only reached after 120 seconds. On the other hand, the addition of 2.3 g iron (III) chloridex6H₂O to the extinguishing water almost leads to a spontaneous reaction. 90 degrees C are reached after only 5 seconds. If 0.4 g of iron (III) chloridex6H₂O and 0.2 g of iron (III) sulfatex7H2O are added to the extinguishing water, the time to reach 90 degrees C is around 50 seconds.

Dieses Beispiel zeigt, daß die hemmende und beschleunigende Wirkung von Mutallsalzen im Löschwasser durch entsprechende Kombinationen gesteuert werden kann.This example shows that the inhibitory and accelerating effects of mutal salts in the extinguishing water can be controlled by appropriate combinations.

Beispiel 6Example 6

28g frisch hergestellter Branntkalk werden mit 18g Wasser gelöscht.
Die Zeit bis zur Erreichung von 90 Grad C beträgt 13 Sekunden. Werden dem Löschwasser 0,4g Aluminiumsulfatx18H₂O zugesetzt, dann werden 18 Sekunden bis zur Erreichung von 90 Grad C benötigt. Die Löschzeit kann um mehr als 50% herabgesetzt werden, wenn der angegebenen Menge von Aluminiumsulfat noch 0,2g Eisen(III)-chloridx6H₂O zugegeben werden. Dann beträgt die erforderliche Zeit zur Erreichung von 90 Grad C nur noch 11 Sekunden.28g freshly made quicklime is extinguished with 18g water.
The time to reach 90 degrees C is 13 seconds. If 0.4 g aluminum sulfate x 18H₂O is added to the extinguishing water, 18 seconds are required to reach 90 degrees Celsius. The extinguishing time can be reduced by more than 50% if the specified amount of aluminum sulfate 0.2 g of iron (III) chloride x 6H 2 O are added. Then the time required to reach 90 degrees C is only 11 seconds.

Claims (2)

Verfahren zur Reinigung von Gasen und Abgasen von sauer wirkenden Gasen, wie Chlorwasserstoff, Fluorwasserstoff, Schwefeldioxid und Blausäure, Stickstoffoxiden, Kohlenwasserstoffen, chlorierten Kohlenwasserstoffen, organischen Verbindungen und flüchtigen Schwermetallen, wie Quecksilber, Arsen, Antimon, Cadmium und Thallium, wobei dem Gas- bzw. Abgasstrom Calciumhydroxid zugemischt wird, dem nach dem Löschen von Branntkalk Aktivkohle, Braunkohlenherdofenkoks, aktiviertes Aluminiumoxid und/oder Kieselgel zugesetzt werden, die Reinigung im Temperaturbereich von 20 bis 1200 Grad C durchgeführt wird und die Abscheidung der Feststoffe an Staubabscheidevorrichtungen erfolgt.Process for the purification of gases and exhaust gases from acidic gases, such as hydrogen chloride, hydrogen fluoride, sulfur dioxide and hydrocyanic acid, nitrogen oxides, hydrocarbons, chlorinated hydrocarbons, organic compounds and volatile heavy metals, such as mercury, arsenic, antimony, cadmium and thallium, the gas or Exhaust gas stream calcium hydroxide is added, to which after the extinguishing of quicklime, activated carbon, lignite stove coke, activated aluminum oxide and / or silica gel are added, the cleaning is carried out in the temperature range from 20 to 1200 degrees C and the solids are separated off using dust separators. Verfahren zur Reinigung von Gasen und Abgasen von sauer wirkenden Gasen, wie Chlorwasserstoff, Fluorwasserstoff, Schwefeldioxid und Blausäure, Stickstoffoxiden, Kohlenwasserstoffen, chlorierten Kohlenwasserstoffen, organischen Verbindungen und flüchtigen Schwermetallen, wie Quecksilber, Arsen, Antimon, Cadmium und Thallium, wobei der Gas- bzw. Abgasstrom mit reaktionsfähigem Calciumhydroxid behandelt wird, welches erhältlich ist durch Löschen von Branntkalk, sowie Zugabe von Aktivkohle, Braunkohlenherdofenkoks, aktiviertem Aluminiumoxid und/oder Kieselgel zu dem gelöschten Branntkalk, die Reinigung im Temperaturbereich von 20 bis 1200 Grad C durchgeführt wird und die Abscheidung der Feststoffe an Staubabscheidevorrichtungen erfolgt.Process for the purification of gases and exhaust gases from acidic gases, such as hydrogen chloride, hydrogen fluoride, sulfur dioxide and hydrocyanic acid, nitrogen oxides, hydrocarbons, chlorinated hydrocarbons, organic compounds and volatile heavy metals, such as mercury, arsenic, antimony, cadmium and thallium, the gas or The exhaust gas stream is treated with reactive calcium hydroxide, which can be obtained by extinguishing quicklime, as well as adding activated carbon, lignite stove coke, activated aluminum oxide and / or silica gel to the extinguished quicklime, cleaning in the temperature range from 20 to 1200 degrees C and the separation of the Solids are carried out on dust separators.
EP95101853A 1987-05-18 1988-05-18 Process for purification of gases and exhaust gases. Withdrawn EP0655273A3 (en)

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DE3716566 1987-05-18
DE19873716566 DE3716566A1 (en) 1987-05-18 1987-05-18 Process for the production of reactive calcium hydroxides for exhaust gas purification
DE19883815982 DE3815982A1 (en) 1987-05-18 1988-05-10 Process for the production of reactive calcium hydroxides for purification of gas and exhaust gas
DE3815982 1988-05-10
DE3816595 1988-05-16
DE3816595 1988-05-16
EP88904222A EP0314733B1 (en) 1987-05-18 1988-05-18 The use of reactive calcium hydroxide for purifying gases and exhaust gases

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EP92103175A Revoked EP0496432B1 (en) 1987-05-18 1988-05-18 Process for cleaning gases and exhaust gases
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EP92103175A Revoked EP0496432B1 (en) 1987-05-18 1988-05-18 Process for cleaning gases and exhaust gases

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ATE137417T1 (en) 1996-05-15
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EP0314733A1 (en) 1989-05-10
EP0496432B1 (en) 1994-08-31
EP0292083A2 (en) 1988-11-23
EP0292083A3 (en) 1989-01-25
EP0496432A1 (en) 1992-07-29
EP0655273A3 (en) 1995-07-26
WO1988009203A2 (en) 1988-12-01
DE8816866U1 (en) 1991-02-28

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